INTRODUCTION
For cement metal restorations, resin cement seems to be a suitable option because it shows the best combination of physical and mechanical properties when compared to zinc phosphate and glass ionomer cements (1). Resin cements can be classified as adhesive or non-adhesive. The adhesive resin cements (e.g. Panavia F, Bistite II, C&B Metabond and Super Bond C&B), in ad-dition to micromechanical retention, contain functional monomers that promote chemical bonding between the cement and the metal surface oxides (2). Whereas the non-adhesive resin cements (e.g. Enforce, Variolink II and RelyX ARC) bond to the surface of metal restorations exclusively by means of micromechanical retention (3). According to Tsuchimoto et al. (4), a strong and durable resin-based material bond to a substrate depends on both micromechanical retention and chemical bond-ing. In cementation with adhesive resin cements, this
Effect of Surface Treatments on the Bond Strength
of a Resin Cement to Commercially Pure Titanium
Antonio Alves de ALMEIDA-JÚNIOR Renata Garcia FONSECA Isabella Gagliardi HANEDA Filipe de Oliveira ABI-RACHED
Gelson Luis ADABO
Department of Dental Materials and Prosthodontics, Araraquara Dental School, São Paulo State University, Araraquara, SP, Brazil
Investigation of the effectiveness of surface treatments that promote a strong bond strength of resin cements to metals can contribute significantly to the longevity of metal-ceramic restorations. This study evaluated the effect of surface treatments on theshear bond strength (SBS) of a resin cement to commercially pure titanium (CP Ti). Ninety cast CP Ti discs were divided into 3 groups (n=30),
which received one of the following airborne-particle abrasion conditions: (1) 50 μm Al2O3 particles; (2) 30 μm silica-modified Al2O3
particles (Cojet Sand); (3) 110 μm silica-modified Al2O3 particles (Rocatec). For each airborne-particle abrasion condition, the fol-lowing post-airborne-particle abrasion treatments were used (n=10): (1) none; (2) adhesive Adper Single Bond 2; (3) silane RelyX Ceramic Primer. RelyX ARC resin cement was bonded to CP Ti surfaces. All specimens were thermally cycled before being tested in shear mode. Failure mode was determined. The best association was Rocatec plus silane. All groups showed 100% adhesive failure. There were combinations that promote higher SBS than the protocol recommended by the manufacturer of RelyX ARC.
Key Words: resin cement, titanium, surface treatment, silica coating, airborne-particle abrasion.
condition can be attained simply by airborne-particle abrasion with aluminum-oxide (Al2O3) particles. In the case of the non-adhesive resin cements, both bonding mechanisms must be created.
For this purpose, metal surface treatments can be used, which are classified into: 1) promoters of micromechanical retention; 2) promoters of chemical bonding and 3) promoters of micromechanical retention and chemical bonding.
Among the promoters of micromechanical reten-tion, airborne-particle abrasion with Al2O3 particles is most widely used (5,6). This procedure cleans the surface and increases the surface area (7). Furthermore, it also decreases surface tension and creates a highly activated surface, favoring the wettability of the substrate by the material applied afterwards (5,6,8). Other surface treat-ments such as roughening with a diamond bur (9) and chemical etching (4,10) also fall into this category. Al-though adhesives have not been mentioned in the
litera-Correspondence: Profa. Dra. Renata Garcia Fonseca, Departamento de Materiais Odontológicos e Prótese, Faculdade de Odontologia de Araraquara, UNESP, Rua Humaitá, no 1680, 4º andar, sala 411, 14801-903 Araraquara, São Paulo, Brasil. Tel: +55-16-3301-6426. Fax: +55-16-3301-6406.
ture as belonging to one of the three existent categories, because of their lower viscosity in comparison with the viscosity of resin cements, they could perhaps provide greater contact between the cement and substrate, thus favoring micromechanical retention.
Chemical bonding can be achieved with metal primers and silanes. Metal primers contain active mono-mers such as MDP, MEPS, 4-META and others that react chemically with the oxides present on the metal surface (11,12). Silanes, due their bifunctional characteristics, establish a chemical bond between the resin matrix and the metal surface (7,13).
Finally, a third category of surface treatment promotes both micromechanical retention and chemical bonding. One known method to achieve both bonding mechanisms is tribochemical silica coating. This method uses airborne-particle abrasion with silica-modified Al2O3 particles in conjunction with silanization (Cojet Sand and Rocatec; 3M ESPE, Seefeld, Germany) (8). Cojet Sand has a particle size of 30 μm, is applied in a single step and is indicated for chairside application with the use of a chairside air abrasion device. Rocatec
has a particle size of 110 μm, requires pre-treatment
by airborne-particle abrasion with Al2O3 particles and was developed for laboratory use. However, there is no reason to contra-indicate its use in the dental office. Considering the importance of an effective bond at the metal/cement interface, as well as the diversity of surface treatments and their possible combinations, the purpose of this study was to evaluate the effect of different surface treatments on the bond strength of a non-adhesive resin cement to commercially pure tita-nium (CP Ti).
MATERIAL AND METHODS
Ninety CP Ti grade II (RMI Co, Niles, OH, USA) discs (9.0 mm in diameter and 3.0 mm thick) were cast in the Discovered Plasma Ar-arc vacuum-pressure cast-ing machine (EDG Equipamentos e Controles Ltd, São Carlos, SP, Brazil) and embedded in a polyvinyl chloride (PVC) tube (20.0 mm in diameter and 27.0 mm high), using polymethyl methacrylate acrylic resin (Clas-Mold; Artigos Odontológicos Clássico Ltd, São Paulo, SP, Brazil). The bonded surfaces of all specimens were smoothed with 150, 400 and 600-grit silicon carbide papers (3M Brazil Ltd, Campinas, SP, Brazil) using a polisher (Metaserv 2000; Buehler UK Ltd, Coventry, England).
The specimens were divided into 3 groups (n=30), which were subjected to one of the following airborne-particle abrasion conditions: 1) 50 µm aluminum-oxide (Al2O3) particles (Bio-Art Equip. Odontol. Ltd., São Carlos, SP, Brazil); 2) 30 µm silica-modified Al2O3 particles (Cojet Sand; 3M ESPE, Germany); 3) 110 µm silica-modified Al2O3 particles (Rocatec; 3M ESPE, Germany). For each airborne-particle abrasion condition, the following post-airborne-particle abrasion treatments were used (n=10): 1) none; 2) adhesive; 3) silane.
Airborne-particle abrasion was performed for 10 s with an airborne-particle abrasive unit (Basic Classic; Renfert GmbH, Hilzingen, Germany), at 4,8 bar pressure, at a 90-degree angle and at a distance of 10.0 mm from the specimen surface. All specimens were ultrasonically cleaned in distilled water for 10 min.
The adhesive Adper Single Bond 2 (3M ESPE, St. Paul, MN, USA) (LOT #51202) was applied, according to manufacturer’s directions, and light-cured for 20 s using a light-curing unit (Curing Light XL 3000; 3M ESPE, USA) at an irradiance of approximately 550 mW/ cm2 and at a distance of 5.0 mm from the specimen sur-face. The silane coupling agent RelyX Ceramic Primer (3M ESPE, USA) (LOT #2721) was applied to the alloy surface with a disposable brush and left to set for 60 s.
For the application of the RelyX ARC resin ce-ment (3M ESPE, USA) (LOT CKCK), a custom-made metal matrix (5.0 mm internal diameter and 2.0 mm thick) was positioned on the surface of the specimen using a centralizing ring attached to the PVC tube. The cement was proportioned by weight. To avoid exposure to daylight (so that there would be chemical activation only), the resin cement was mixed in accordance with the manufacturer’s instructions and inserted into the matrix inside a radiographic developing chamber (Odontologic Indústria e Comércio Ltd, São Paulo, SP, Brazil).
Forty minutes after preparation, all specimens were stored in distilled water at 37ºC for 24 h before thermal cycling between 5ºC and 55ºC for 5,000 cycles with a 30-s dwell time. Specimens were tested for shear bond strength (Fig. 1) using a testing machine (810 Ma-terial Test System; MTS Systems Corp, Eden Prairie, MN, USA), with a 1 kN load cell. A knife-edge-shearing rod running at a crosshead speed of 0.5 mm/min was used to load the specimens until fracture. Shear bond strength values were recorded in MPa.
were captured by a computer software (Leica Applica-tion Suite EZ; Leica Microsystems Ltd). Failure mode was recorded by a single calibrated observer as either adhesive (between metal and resin cement), cohesive (within the resin cement) or combination (areas of ad-hesive and coad-hesive failure). For this classification, the adhesive area was divided into quadrants, and in each of them, the predominant type of fracture was observed. According to the method of Santos et al. (14), the fracture was classified as adhesive or cohesive if either of these types predominated in 3 or more quadrants, and classi-fied as combination if 2 quadrants presented adhesive failure and the other 2 cohesive failure.
Data were analyzed using a 2-way ANOVA fol-lowed by Tukey’s multiple-comparison test at a level of
significance of α=0.05, with airborne-particle abrasion
condition (50 µm Al2O3 particles; Cojet Sand; Rocatec) and post-airborne-particle abrasion treatment (none; adhesive; silane) as factors.
RESULTS
The results of the two-way ANOVA revealed that airborne-particle abrasion, post-airborne-particle abra-sion and their interaction were significant (p<0.001).
Table 1 shows the mean shear bond strength val-ues and standard deviations for each group and statisti-cal results. When the factor airborne-particle abrasion
condition was investigated, there was no significant
difference (p>0.05) between 50 µm Al2O3 particles and Rocatec, but both conditions showed higher bond strength than Cojet Sand (p<0.05). When the factor
post-airborne-particle abrasion treatment was investigated,
there was significant difference among the 3 treatments
(p<0.001), with silane having promoted the highest bond strength. The lowest bond strength was found when no post-airborne-particle abrasion treatment was used. With regard to the significant interaction be-tween airborne-particle abrasion condition and post-airborne-particle abrasion treatment (p<0.001), in the post-airborne-particle abrasion treatment with silane, in which there is chemical bonding, the airborne-particle abrasion with 50 µm Al2O3 particles exhibited lower bond strength than Cojet Sand and Rocatec (p<0.05). When no post-airborne-particle abrasion treatment was used, there was no significant difference (p>0.05) between Rocatec and Cojet Sand. In the groups abraded with 50 µm Al2O3 particles, the adhesive was the best post-airborne-particle abrasion treatment (p<0.001), there having been no significant difference (p>0.05) between the group treated with silane and the group that did not receive post-airborne-particle abrasion treatment. In the airborne-particle abrasion with Cojet Sand, there was no significant difference (p>0.05) between the group treated with adhesive and the group that did not receive post-airborne-particle abrasion treatment.
Rocatec plus silane was the combination of airborne-particle abrasion condition and post-airborne-particle abrasion treatment that promoted the highest bond strength. No significant difference (p>0.05) was found between 50 µm Al2O3 particles plus adhesive and Cojet Sand plus silane (p>0.05). All groups showed 100% adhesive failure.
DISCUSSION
The guidelines for cementing with RelyX ARC
Table 1. Mean shear bond strength values (standard deviations) (MPa) and statistical results.
Post-airborne-particle abrasion treatments
Airborne-particle abrasion conditions
50 µm Al2O3
Cojet Sand 50 µm Al2O3 + Rocatec
None 4.10
(0.79) Ba
2.58 (0.37) Bb
3.65 (0.70) Cab
Adhesive 6.14 (0.99) Aa
2.31 (0.23) Bb
5.25 (1.08) Ba
Silane 4.34 (0.71) Bc
5.70 (0.93) Ab
8.36 (1.63) Aa
resin cement recommend only the application of a si-lane coupling agent on the inner surface of previously Al2O3 airborne-particle abraded metal restorations. In the present study, the efficacy of alternative surface treatments was investigated, providing situations with micromechanical retention only and also with both bonding mechanisms.
In all the situations in which there was only micromechanical retention (no silane coupling agent), there was no significant difference between airborne-particle abrasion with 50 µm Al2O3 particles and Rocatec. However, both conditions showed higher bond strength than Cojet Sand, except when no post-airborne-particle abrasion treatment was used; in this situation, there was statistical equality between Cojet Sand and Rocatec.
Although there were particles with different chemical compositions among the airborne-particle abrasion conditions used in this study, as there was a condition of Al2O3 particles only (50 µm particles) and two of silica-modified Al2O3 particles (Cojet Sand and Rocatec), a possible explanation for the results obtained, would be the particle size.
Some studies (15-19) have shown evidence of the influence of particle size on the bond strength of resin-based materials to metals. Several authors (15-17) found significantly higher bond strengthwith smaller Al2O3 particles compared to larger sized Al2O3 particles. However, the influence of this factor on titanium was not evaluated in any of these three studies. Other studies (18,19) haveevaluated the bond strength of resin-based materials to CP Ti and have shown exactly the opposite; that is, larger Al2O3 particles promoted higher mean shear bond strength than the smaller particles. Papadopoulos et al. (18) observed that larger Al2O3 particles increase the roughness of the CP Ti surface, making it more favorable to micromechanical retention.
The statistical equality observed between the airborne-particle abrasion with 50 µm Al2O3 particles and with Rocatec could have been the result of previ-ous airborne-particle abrasion, also with 50 µm Al2O3 particles, performed in Rocatec. Based on previous studies (18,19),if this previous airborne-particle abra-sion in Rocatec had been done with 110 µm Al2O3 particles; that is with particlesof the same size as the silica-modified Al2O3 particles of Rocatec, it may be that this silica coating system may have been superior to the airborne-particle abrasion with 50 µm Al2O3 par-ticles. This same line of reasoning could also be used to justify the superiority of the 50 µm Al2O3 particles and
of Rocatec over Cojet Sand, which has a smaller sized particle (30 µm).
On the other hand, in the situations in which there was both micromechanical retention and chemical bond-ing, both silica coating systems (Cojet Sand and Rocatec) exhibited significantly higher bond strength than the airborne-particle abrasion with 50 µm Al2O3 particles. Therefore, when the silane coupling agent was used, the chemical composition of the particles (silica-modified or not) was a more decisive factor in bond strength than the particle size. Nevertheless, Rocatec (110 µm) promoted significantly higher mean shear bond strength than Cojet Sand (30 µm), which is in agreement with the findings of previous investigations (18,19).
As regards the superiority of silane compared to no post-airborne-particle abrasion treatment and adhe-sive, this behavior could be justified by the chemical bonding this material promotes, since it is an additional bonding mechanism, as the airborne-particle abrasion already promotes micromechanical retention. Silanes es-tablish a chemical bond between the resin matrix and the metal surface due their bifunctional characteristics. The non-hydrolysable organic group contains carbon-carbon double bond which can polymerize with monomers of the resin-based materials. The hydrolysable groups react with an inorganic hydroxyl-rich (-OH) surface such as silica-coated (SiO2) metal surfaces (7,13). This justifies the superiority of silane in the groups abraded with Cojet Sand and Rocatec, observed in the present study.
On the other hand, in the groups airborne-par-ticle abraded with 50 µm Al2O3 particles, the adhesive promoted significantly higher bond strength than the silane. Papadopoulos et al. (18) observed that when airborne-particle abrasion with 50 µm Al2O3 particles was performed, high alumina contamination of the CP Ti surface was detected. According to Matinlinna et al. (7), if alumina is embedded into a substrate, it provides
hydrolytically unstable =Al-O-Si≡ bonds which are weaker than ≡Si-O-Si≡ bonds.
the cement is applied directly on the airborne-particle abraded surface. In the groups abraded with Cojet Sand, the statistical equality observed between the adhesive and no post-airborne-particle abrasion treatment, could have occurred due to less surface roughness resulting from the airborne-particle abrasion with 30 µm particles; that is, it does nothing to increase contact of the cement with a surface that is not very rough.
Finally, three combinations achieved significantly higher bond strength than the protocol recommended by the RelyX ARC manufacturer, as the four situations presented a predominance of adhesive failure. One of the combinations was the airborne-particle abrasion with Rocatec plus silane, which provided the high-est bond strength. As pre-treatment, Rocatec requires airborne-particle abrasion with 110 µm Al2O3 particles. Although this pre-treatment was performed with 50 µm Al2O3 particles in the present study, it still presented the highest bond strength. Further studies must be con-ducted to investigate the effect of different Al2O3 particle sizes used for pre-treatment as well as the effect of not performing this pre-treatment, on the bond strength of resin cements to metal surfaces abraded with Rocatec. Moreover, although this system having been developed for laboratory use, the inner surface of restorations can be airborne-particle abraded with Rocatec by using a chairside air abrasion device.
Ranked second, there is airborne-particle abrasion with 50 µm Al2O3 particles plus adhesive (micromechani-cal retention only) and airborne-particle abrasion with Cojet Sand plus silane (both bonding mechanisms), which were statistically equal to each other. This sta-tistical equality, as well as the superiority of 50 µm Al2O3 particles plus adhesive when compared with the protocol recommended by the manufacturer of RelyX ARC, indicate that certain combinations of treatments that favor micromechanical retention may be capable of producing bond strengths that are as strong as those resulting from treatments that promote both bonding mechanisms.
This study showed evidence of the superiority of some of the combinations to others, with decisive factors in determining the bond strength being the particle size under certain conditions and the chemical composition of the particles in others. Nevertheless, there are some factors that were not considered in the present study, which can influencing the bond strength of resin ce-ment to CP Ti. Therefore, careful interpretation in the clinical application of the results is suggested. Studies
that evaluate factors simulating the conditions of the oral cavity, such as long-term water storage, dynamic fatigue loading and pH changes should be carried out to affirm whether or not the evaluated combinations are effective (20).
Within the limitations of an in vitro study, the fol-lowing conclusions were drawn: (1) with regard to the existence of exclusively micromechanical retention, the airborne-particle abrasion with 50 µm Al2O3 particles and Rocatec promoted bond strengths that were equal to each other, and higher than those promoted by Cojet Sand; (2) in the post-airborne-particle abrasion treatment with silane, the airborne-particle abrasion with 50 µm Al2O3 particles exhibited the lowest bond strength and Rocatec, the highest SBS; (3) in general, Rocatec exhibited higher SBS than Cojet Sand; (4) silane was indispensable after airborne-particle abrasion with Rocatec and Cojet Sand; (5) three combinations presented higher SBS than that of the RelyX ARC manufacturer’s protocol.
RESUMO
A investigação da eficácia de tratamentos de superfície que promovem uma forte resistência de união de cimentos resinosos aos metais pode contribuir significantemente para a longevidade das restaurações metalocerâmicas. Este estudo avaliou o efeito de tratamentos de superfície na resistência ao cisalhamento da união de um cimento resinoso ao titânio comercialmente puro (Ti cp). Noventa discos foram fundidos em Ti cp e divididos em 3 grupos (n=30), os quais receberam uma das seguintes condições de jateamento: (1) partículas de Al2O3 de 50 μm; (2) partículas de Al2O3 modificadas por sílica de 30 μm (Cojet Sand); (3) partículas de Al2O3 modificadas por sílica de 110 μm (Rocatec). Para cada condição de jateamento, os seguintes tratamentos pós-jateamento foram utilizados (n=10): (1) nenhum; (2) adesivo Adper Single Bond 2; (3) silano RelyX Ceramic Primer. O cimento resinoso RelyX ARC foi aplicado à superfície do Ti cp. Todos os espécimes foram termociclados antes do ensaio de cisalhamento. O modo de fratura também foi determinado. A melhor associação foi o Rocatec mais silano. Todos os grupos apresentaram 100% de falha adesiva. Houve combinações que promoveram maior resistência ao cisalhamento da união que aquela recomendada pelo fabricante do RelyX ARC.
ACKNOWLEDGEMENTS
This investigation was supported by the São Paulo State Research Foundation (FAPESP - Grant #07/06972-3).
REFERENCES
2. Schneider R, de Goes MF, Henriques GEP, Chan DCN. Tensile bond strength of dual curing resin-based cements to commercially pure titanium. Dent Mater 2007;23:81-87.
3. Ozcan M, Pfeiffer P, Nergiz I. A brief history and current status of metal-and ceramic surface-conditioning concepts for resin bond-ing in dentistry. Quintessence Int 1998;29:713-724.
4. Tsuchimoto Y, Yoshida Y, Takeuchi M, Mine A, Yatani H, Tagawa Y et al. Effect of surface pre-treatment on durability of resin-based cements bonded to titanium. Dent Mater 2006;22:545-552. 5. Kern M, Thompson VP. Sandblasting and silica-coating of dental
alloys: volume loss, morphology and changes in the surface com-position. Dent Mater 1993;9:155-161.
6. Kern M, Thompson VP. Effects of sandblasting and silica-coating procedures on pure titanium. J Dent 1994;22:300-306.
7. Matinlinna JP, Vallittu PK. Silane based concepts on bonding resin composite to metals. J Contemp Dent Pract 2007;8:1-8. 8. Bertolotti RL. Adhesion to porcelain and metal. Dent Clin North
Am 2007;51:433-51.
9. Cobb DS, Vargas MA, Fridrich TA, Bouschlicher MR. Metal sur-face treatment: characterization and effect on composite-to-metal bond strength. Oper Dent 2000;25:427-433.
10. Fawzy AS, El-Askary FS. Effect acidic and alkaline/heat treat-ments on the bond strength of different luting cetreat-ments to com-mercially pure titanium. J Dent. 2009;37:255-263.
11. Taira Y, Matsumura H, Yoshida K, Tanaka T, Atsuta M. Adhesive bonding of titanium with a methacrylate-phosphate primer and self-curing adhesive resins. J Oral Rehabil 1995;22:409-412. 12. Yoshida K, Taira Y, Matsumura H, Atsuta M. Effect of adhesive
metal primers on bonding a prosthetic composite resin to metals.
J Prosthet Dent 1993;69:357-362.
13. Matinlinna JP, Lassila LVJ, Vallittu PK. The effect of five silane coupling agents on the bond strength of a luting cement to a silica-coated titanium. Dent Mater 2007;23:1173-1180.
14. Santos JG, Fonseca RG, Adabo GL, Cruz CAS. Shear bond strength of metal-ceramic repair systems. J Prosthet Dent 2006;96:165-173.
15. Mukai M, Fukui H, Hasegawa J. Relationship between sandblast-ing and composite resin-alloy bond strength by a silica coatsandblast-ing. J Prosthet Dent 1995;74:151-155.
16. Petridis H, Garefis P, Hirayama H, Kafantaris NM, Koidis PT. Bonding indirect resin composites to metal: part 2. Effect of alloy surface treatment on elemental composition of alloy and bond strength. Int J Prosthodont 2004;17:77-82.
17. Sarafianou A, Seimenis I, Papadopoulos T. Effectiveness of different adhesive primers on the bond strength between an indirect composite resin and a base metal alloy. J Prosthet Dent 2008;99:377-387.
18. Papadopoulos T, Tsetsekou A, Eliades G. Effect of aluminium oxide sandblasting on cast commercially pure titanium surfaces. Eur J Prosthodont Rest Dent 1999;7:15-21.
19. Watanabe I, Kurtz KS, Kabcenell JL, Okabe T. Effect of sandblast-ing and silicoatsandblast-ing on bond strength of polymer-glass composite to cast titanium. J Prosthet Dent 1999;82:462-467.
20. Mair L, Padipatvuthikul P. Variables related to materials and pre-paring for bond strength testing irrespective of the test protocol. Dent Mater 2010;26:e17-e23.
